Vat dyestuff



Patented Apr. 22, 1930 ITE SIGNORS TOGENERAL ANILINE WORKS, INCL,

TION OI DELAWARE on NEW YOR N. 2., A CORPORA- VA'J. DYESTUFF No Drawing. Application filed May 22, 1928, Serial No. 279,846, and in Germany May 30, 1927.

Our presentinvention relates -to new sulfur-containing vat dyestuffs, more particularly to dyestuffs containing the following general atomic grouping z,

alkyl-O 0 v am wherein X stands for hydrogen or halogen.

We have found that valuable dyestulfs of the thioindigo series and, of the thionaphthene-indolindigo series are obtained by converting an oxythionaphthene of the general formula:

6 \OH2 x s alkylthe actiono-fan oxidizing agent into the symmetrical thioindigo dyestufl or causing it to react with such a body as is capable of forming Vat dyestuffs with oxythionaphthenes as for instance an ortho-diketone or an a-dGIlV- ative therof.

The dyestuffs may also be prepared by first transforming the new o-x'ythionaphthenes into their (Jr-derivatives, for instance by means of nitrosodimethylaniline into; the 2-aniles,

indo xyl or the like.

The new (1 estuffs correspond to tli e followalk l-o wherein X stands for hydrogen or halogen, Z for sulfur or the NH-group and R for an aromatic residue of the benzene-, naphthachlorine.

leneor anthracene series which may be substituted in any manner.

The new dyestuffs are distinguished by a remarkable fastness to Washing, light and The dialkoxy-hydroxythionaphthenes used in the process of this invention have hitherto been unknown. They can be prepared in an easy and smooth reaction in the following manner: a x

By treatin the 3.5-dihydroxybenzoic acid with an alky lating agent the corresponding alkoxybenzoic acid is obtained. The latter is nitrated, the nitro group entering the orthoposition to the carboxyl group.

The dialkoxyl-nitro-benzoic acid thus obtained of the general formula:

alkyl-O OOOH X N 02 alkylwherein X stands for hydrogen or a halogen,

is reduced to the corresponding substituted amino compound and the latter is transformed into the correspondingly substituted aryl-thio-glycolcarboxylic acid. This dialkoxy-phenyl-thioglycolcarboxylic acid of the general formula:

wherein X stands for hydrogen or a halogen,

'is transformed into the alkoxy-oxythionaphthem by treating it with an alkaline condensing agent 'as. for instance caustic soda, and splitting. 'otf carbon dioxide from the dialkoxy-oxythionaphthene-carboxylic acid, which is at first formed, by means of an .acid agent, or by treating it with acetic anhydride and subsequently splitting ofl the acetyl group which .has entered, I

The 5.7 -dir'nethoxy-3-oxythionaphthene can for example be prepared in the following manner:

By nitrating 3.5-dimethoxy-benz0ic acid,

the 3.5-dimethoxy-2-nitro-benzoic'acid of the formula:

formula omo coon is .obtained. It forms in a pure state nearly. colorless crystals melting at 232 C. On storage the crystals quickly" assume at first a yellow and afterwards a turbid green colora-- tion. L'

The said nitro-carboxylic acid is reduced in the usual manner to the 3.5-dimethoxy-2- amino-carboxylic acid, which crystallizes from alcohol in the form of nearly colorless needles melting at 189 C. to 190 C.

The 3.5-dimethoxy-phenyl 2-thioglycol-1- carboxylic acid obtainable therefrom of the crystallizes from water in the form of colorless needles. The compound meltsat 105 C.,

to 107 0., probably while losing crystal 'water, then-re-solidifies and melts again at 128 C. to 130 C. I

This thioglycol-carboxylic acid is transformed in known manner into the 5.7-dimethoxy-3-oxythionaphthene of the formula It crystallizes from dilute alcohol in the form of fine yellowish needles melting at 143 C. It "dissolves in alcohol and glacial acetic acid with a green, in benzene with a blue fluorescence.

The 5.7-diethoxy-3-.oxythionaphthene of the'formula:

is prepared in the same manner by starting from the 3.5-diethoxy-benzoic acid. It crystallizes'from dilute acetic-acid in the form of ellowish laminae melting at 103 C.

he dialkoxyl-halogen-pheriyl-thioglycolcarboxylic acids of the general formula:

are obtained by treating with a halogenating agent the dialkoxyl-phenyl-thioglycolcarboxylic acids or the corresponding substi-' tuted starting products.

Thus the -3.5-dimethoxyi-bromo-phenyl- 2-thioglycol-1-carboxylic acid of the formula:

c1180 are dissolved in 18 partsof caustic soda solution of 40 B. and 200 parts of water. Into this solution is run, while stirring, a solution of 80 parts of potassium ferricyanide in 300 parts ofwater. The dyestufi' separates asa fine blue precipitate. After having further stirred for half an hour, the dyestuif is filtered by suction, washed with water and dried. It has the formula:

CH] C 0\ /C 0 00B; 0:0 8 S OH; CH;

It isin adry state a dark blue powder which dissolves in cold concentrated sulfuric acid to an orange-red solution with a like fluorescence, in warm concentrated sulfuric acid to a reddish-violet solution. The solution in nitrobenzene is pure blue.

The dycstufi forms with alkaline hydrosulfite an olive-green vat from which cotton and wool are dyed bluish-gray fast tints.

A dyestuff of similar tinctorial properties is obtained by oxidizing in the same manner 24 parts of 5.7 -diethoxy'-3-oxythionaphthene with potassium ferricyanide. The dyestufl' has the'following constitution:

The colorations of its solutions are the same as those of the above-described methoxy derivative. In the form of a owder it has a dark blue appearance. It yields with alka- .which cotton and wool are line hydrosulfite an olive-(green vat from yed bluish-gray tints.

"By substituting in the above example for the 5.7-dimethoxy-3-oxythionaphthene 29 parts of 5.7-dimethoxy-6-bromo-3-oxythiolowish-o live vat viole t tints. In'the form of a powder the dyestufi is brownish-violet. It is soluble in cold concentrated sulfuric acid to a bluish-green, in warm concentrated sulfuric acid to a pure green solution. Thecolor of its solution in nitrobenzeneis reddish-violet. 79 (3) A' mixture of 27 parts of 3.5- dime-.

naphthene there is obtained a dyestufi having .thoxy-phenyl-2-thioglycol-l-carboxylic acid, the formula: 33 parts of 2- (para-dimethylamino)-anile of 4-methyl-6 chloro 2.3 diketo-dihydrothionaphthene and 400 parts of acetic anhydride 75 is heated for about one hour to boiling in a B J reflux condenser. The mixture first dissolves v cm cm andsolidifies after a short time to aviolet crystalline magma which. after cooling is 15. The dyestuff forms, when dried. a dark blue filtered by'suction. The dyestufi' is'purified 9" powder. It dissolves in cold concentrated by boiling with alcohol or glacial acetic acid. sulfuric acid to aturbid yellowish-green solu- It is identical with that obtainable according .tion which on heating turns into a reddishto Example 2. I v blue. The color of the solutionin nitro'ben- (4) 21 parts of 5.7-dimethoxy-3-oxythiozene is greenish-blue. 1 f naphthene and 32 parts of 2- (para-dimethyl- 5.

By treating the dyestuff in the usual manamino)-anile of 2.3-naphthoxythiophene. are ner with an alkaline hydrosulfite'solution, it dispersed in about 400 parts of glacial acetic forms a'rather sparingly soluble and almost acid or chlorobenzene or in another suitable colorless leuco compound in which vat cotton dissolving or suspending agent. The mixture and woolare dyed faint blue tints. v is heated, while stirring, until the'formation I (2) 21 parts of 5 .7-dimethoxy-3-oxythioof the dyestuff' is complete. The dyestuif naphthene and 33 parts of 2'- (paraedimethylfprms grayish-violet crystals. After cooling amino) -anile o 4-methyl-6-chloro-2.3-diket0- it is filtered by suction and boiled with alcohol dihydrothionaphthene-are dispersed'in'abo'u't or glacial aceticacld so as to purify it; The 3 400 parts of. glacial acetic acidor chlorobenformation of the dyestufi takes place accordzene or in another appropriate dissolving or ing to the following equation: v

- ohm *Co\ I j o/co' -CH2+( a):N 35 s/ \S a omo oo\ /oo 7 =0 oB'amO-NH, 4 v '10s- CH3 v I I I suspending agent. The mixture is then heat- The dyestuif' dissolves in concentrated suled, while stirring, until the formation of the furic acid to a green, 1n nitrobenzene to a blue is dyestuff is complete. The dyestuf'f separates solution. It gives w th'alkallne hydrosulfites no in the form ofi violet crystals whichafter reddish-brown vats n which cotton and wool cooling are filtered by suction and are boiled are dyed a dark blulsh-gray tint. out with glacial acetic acid or with alcohol in (5) 21.6 parts of 5.7 -dichlorisatm and 24 order to purify them. I parts of phosphorus pentachloride are dis- 59 The dyestufi is formed according to the persed in 200 parts of benzene. The mixture following equation: I is heated to bo1l1ng1na reflux apparatus' unon; 011,0 'oo\ V 5: cna+tcnom I -N= I 0H; 00 co 5/ I l I I CHap The dyestuif dyescotto'n and wool from a yeltil the formation of the chlorideisconiplete. This solution'is run,. whilestirring into a of Violet crystals.

warm solution'of 21 parts of 5.7 -dimethoxy- 3-oxythionaphthene in 300 parts of alcohol. The dyestufi' precipitates at once in the form In order to finish the condensation the mass 15 heated on the steam bath for half an hour. The dyestuff is filtered'by suction, boiled with alcohol and dried.

The following equations shows the course of the reaction taking place in the formation of the present dyestufi 01 oo' 01 co o+ro1h x1411 NH CH O ' The dyestufi' dissolves in concentrated sulwherein X stands for hydrogen or halogen, Z for sulfur or the NH-group and R for an aromatic residue of the benzene-, naphthaleneor anthracene series which may be substituted in any manner.

2. As new products, the vat dyestuffs of the following formula:

Eli

alkyl wherein Z stands for sulfur or the NH-group and R for an aromatic residue of the benzene-, naphthaleneor anthracene series which may be substituted in any manner.

3. As new products, the vat dyestuffs of the following formula:

wherein X stands for hydrogen or halogen.

4. As a new product, the vat dyestufi of the following formula:

o o om-o i 0-011: 51 s V -on, -cn.

being a dark-blue powder, forming with alkaline hydrosulfite an olive-green vat, from which cotton and wool are dyed bluish-gray fast tints.

In testimony whereof, we aflix our signatures.

KARL SCHIRMACHER. KARL EISHOLD. 

